US20140060163A1 - Liquid sending pipe for liquid chromatograph detector and liquid chromatograph - Google Patents
Liquid sending pipe for liquid chromatograph detector and liquid chromatograph Download PDFInfo
- Publication number
- US20140060163A1 US20140060163A1 US14/012,227 US201314012227A US2014060163A1 US 20140060163 A1 US20140060163 A1 US 20140060163A1 US 201314012227 A US201314012227 A US 201314012227A US 2014060163 A1 US2014060163 A1 US 2014060163A1
- Authority
- US
- United States
- Prior art keywords
- liquid
- pipe
- temperature
- liquid chromatograph
- detector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/6416—With heating or cooling of the system
Definitions
- the present invention relates to a liquid sending pipe for a liquid chromatograph detector and a liquid chromatograph.
- a sample is injected into a column, and components of the sample are temporally separated using a difference in the affinity and a distribution state of the components of the sample to two phases of a stationary phase and a mobile phase.
- Each component is eluted from the column, then passes through a pipe together with the mobile phase, and is introduced into a detector to be subjected to an analysis.
- optical detectors such as an absorbance detector and a fluorescence detector are most frequently applied for reasons of a wide application range thereof and the like.
- the column and the detector are each modularized, modules suited to an analysis purpose are selected and combined, and the modules are connected by a pipe, whereby desired performance is obtained.
- the temperatures of the modularized column and the modularized detector are controlled independently of each other.
- JP-A 2010-48554 discloses a technique of controlling the temperature of a column.
- the column is housed inside of a constant temperature bath, and a temperature sensor is attached to the outer surface of the column. Electric current supplied to a heater provided in the constant temperature bath is controlled such that a value of the temperature sensor is a target temperature, whereby the temperature of the column (that is, the temperature of a mobile phase) is controlled.
- JP-A 2008-256530 discloses a technique of controlling the temperature of a detector.
- a flow cell is irradiated with light emitted from a light source, and the amount of transmitted light is detected by a photodetector.
- This configuration includes: a sample temperature regulation block for housing the flow cell therein; and a photodetector temperature regulation block for housing the photodetector therein, and also includes a simultaneous temperature regulation block in contact with the two blocks. Then, the simultaneous temperature regulation block is regulated to a constant temperature, whereby the temperature of a mobile phase supplied to the flow cell and the temperature of the photodetector are kept constant.
- a pipe is necessary to send a mobile phase containing a sample from a column module to a detector module, and the temperature of the mobile phase fluctuates under influences of surrounding environments also when the mobile phase passes through the pipe between the column module and the detector module.
- a pipe winding unit 42 is provided in the detector module separately from a pipe 41 , and the pipe winding unit 42 is placed in close contact around a temperature regulation block.
- a region sandwiched between two double wavy lines in FIG. 4 shows the inside of a temperature regulation block 46 , where a light source 45 , a flow cell 43 , and a photodetector 44 are provided.
- the temperature of the mobile phase is made constant by heat exchange with the temperature regulation block and the like when the mobile phase passes through the pipe winding unit 42 . Accordingly, the temperature of the mobile phase supplied to the flow cell 43 is always constant, and the output of the photodetector 44 can be prevented from being influenced.
- the heat capacity of the mobile phase passing through a pipe between a column module and a detector module decreases, and influences of surrounding environments thereon increase.
- the temperature of the mobile phase detected by the detector is more stable.
- An objective of the present invention is to provide a liquid sending pipe for a liquid chromatograph detector and a liquid chromatograph that are capable of always keeping the temperature of a sample component at the time of detection by the detector constant and thus preventing an influence of the temperature on the output of the detector, in a low flow rate analysis using a modularized column unit and a modularized detection unit.
- the present invention achieved to solve the aforementioned problems provides a liquid sending pipe for a liquid chromatograph detector, the liquid sending pipe being used for a liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid sending pipe including:
- connection pipe for introducing a sample eluted from the column of the column module into the detection unit module
- connection pipe b) a heat insulating member for covering an outer circumference of the connection pipe.
- the heat insulating member may include: an air layer for covering the outer circumference of the connection pipe; and a tube for covering the air layer. With this configuration, an excellent heat insulating effect of air can be used.
- the heat insulating member may include a sealing member for sealing the air layer between the connection pipe and the tube.
- the heat insulating member may include a sponge for covering an outer circumference of the tube, whereby a more excellent heat insulating effect can be obtained.
- the invention of the present application also provides a liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid chromatograph including:
- connection pipe provided between the constant temperature bath and the detection unit module
- connection pipe b) a heat insulating member for covering an outer circumference of the connection pipe.
- a lowest flow rate in a measurement range is equal to or less than 1 ⁇ L/min.
- the temperature of the connection pipe is insusceptible to influences of surrounding environments due to the heat insulating effect of the heat insulating member that covers the outer circumference of the connection pipe.
- the column exterior volume (here, refers to “the volume of a flow path in which a sample component is eluted from the column and is supplied to a flow cell”) can be reduced by removing the pipe winding unit.
- effects outside of the column such as peak broadening, can be reduced, and an increase in speed and resolution of the liquid chromatograph can be achieved.
- FIG. 1 is a configuration diagram of a main part of a liquid chromatograph according to an embodiment of the present invention.
- FIG. 2 is a configuration diagram of a liquid sending pipe for the liquid chromatograph detector according to the present embodiment.
- FIG. 3 is a detailed diagram of the liquid sending pipe for the liquid chromatograph detector according to the present embodiment.
- FIG. 4 is a schematic diagram of a conventional liquid chromatograph detector.
- FIG. 5A is a graph showing an experiment result when a liquid sending pipe of the present invention is not used
- FIG. 5B is a graph showing an experiment result when the liquid sending pipe of the present invention is used.
- FIG. 1 is a configuration diagram of a main part of a liquid chromatograph according to the present embodiment.
- a column 21 that separates each component of a sample is housed in a temperature-regulated constant temperature bath 20 .
- a fan for agitation 22 and a heater for heating 23 are provided inside of the constant temperature bath 20 .
- a temperature sensor 24 is provided on a surface of the column 21 to regulate the temperature to be constant.
- a detection unit module 30 includes a temperature regulation block 34 , and the temperature of the temperature regulation block 34 is regulated by a heater, a temperature sensor, and the like, which are not shown.
- a region sandwiched between two double wavy lines in FIG. 1 represents the inside of the temperature regulation block 34 , and a light source 33 , a flow cell 31 , and a photodetector 32 are provided inside thereof.
- Sample components eluted from the column 21 and a mobile phase reach the detection unit 30 through a connection pipe 11 , and are then supplied to the inside of the flow cell 31 .
- the flow cell 31 is irradiated with light from the light source 33 , the transmitted light is detected by the photodetector 32 , and the detection result is converted into light absorption characteristics of the sample components.
- the analysis is not limited to such measurement of light absorption characteristics, but other characteristics such as fluorescence characteristics may be measured.
- an outer circumference of the connection pipe 11 between the column module 25 and the detection unit module 30 is covered with a tube 12 ( FIG. 1 ). That is, an air layer 15 is formed between the connection pipe 11 and the tube 12 , and a heat insulating member 13 made of the air layer 15 and the tube 12 is provided on the outer circumference of the connection pipe 11 ( FIG. 2 ). Further, a sealing member 14 is provided at each end of the connection pipe 11 , whereby the air layer 15 is sealed between the connection pipe 11 and the tube 12 ( FIG. 3 ).
- the sealing member may be formed by, for example, using a heat-shrinkable tube as the tube 12 and heating and shrinking each end of the heat-shrinkable tube. Moreover, in order to enhance a heat insulating effect, the outer circumference of the tube 12 may be covered with a sponge or the like.
- a PEEK pipe having a heat conductivity that is about one tenth (0.25 to 0.92 W/(m ⁇ k)) of that of the stainless-steel pipe is used therefor, heat insulation properties can be enhanced.
- the inner diameter of the PEEK pipe was 0.13 mm, the outer diameter thereof was 1.6 mm, and the length of the pipe was 430 mm.
- a Sumitube (registered trademark) that is a heat-shrinkable tube was used as the tube of the liquid sending pipe of the invention of the present application.
- the inner diameter of the Sumitube was 2.1 mm, the thickness thereof was 0.2 mm, and an air layer having a thickness of 0.25 mm was formed between the PEEK pipe and the Sumitube.
- the flow rate of the mobile phase of the liquid chromatograph was set to 0.6 mL/min. Further, the capacity of the flow cell and the capacity of the pipe from the column to the flow cell were each set to about one tenth of that in conventional techniques.
- the experiments were carried out in a room.
- the temperature of the room during the experiments slowly changed in a cycle of approximately 30 minutes due to turning on/off of an air conditioner.
- the fluctuation range of the room temperature at that time was about 2° C.
- a solution containing acetonitrile, water, and triethylamine at a ratio of 500:500:1 was used as the mobile phase of the liquid chromatograph.
- Triethylamine is capable of great absorption in a short wavelength region around 230 nm, and the amount of its absorption increases as the temperature rises.
- the mobile phase used for the experiments of this time had an absorption wavelength at 230 nm.
- data was acquired for four cases where the light wavelength of the detector used for the analysis was 350 nm, 300 nm, 250 nm, and 230 nm.
- FIG. 5A and FIG. 5B are graphs in which the horizontal axis is time (minute) and the vertical axis is an absorbance unit (AU) calculated from the detection intensity of the detector.
- the detection intensity fluctuates in a relatively long cycle (about 30 minutes) (baseline fluctuation). This cycle is coincident with the fluctuation cycle of the room temperature, and it can be understood that the temperature of the mobile phase inside of the connection pipe 11 is influenced by surrounding environments (room temperature). It can also be understood that the detection intensity fluctuates in a cycle shorter than that of the baseline fluctuation. This is considered as noise that is generated because the temperature of the mobile phase inside of the connection pipe is influenced by local fluctuations of an air convection in the liquid chromatograph.
- the baseline fluctuation and the noise are larger at the absorption wavelength (230 nm) of the mobile phase.
- Table 1 shows numerical values of the baseline fluctuation and the noise in FIG. 5A and FIG. 5B .
- values of the baseline fluctuation are calculated from a difference between a local maximum value and a local minimum value of the detection intensity in each graph.
- values of the noise are calculated on the basis of ASTM standards E1657-96, in order to eliminate an influence of the baseline fluctuation.
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Optical Measuring Cells (AREA)
Abstract
A heat insulating member 13 is provided on the outer circumference of a connection pipe 11. The heat insulating member 13 includes: a tube 12; and an air layer 15 between the connection pipe 11 and the tube 12. Accordingly, it is possible to always keep the temperature of a sample component at the time of detection by a detector constant and thus prevent an influence of the temperature on an output result of the detector, in a low flow rate analysis using a modularized column unit and a modularized detection unit.
Description
- The present invention relates to a liquid sending pipe for a liquid chromatograph detector and a liquid chromatograph.
- In a liquid chromatograph, a sample is injected into a column, and components of the sample are temporally separated using a difference in the affinity and a distribution state of the components of the sample to two phases of a stationary phase and a mobile phase. Each component is eluted from the column, then passes through a pipe together with the mobile phase, and is introduced into a detector to be subjected to an analysis.
- Various methods are applied to the detector. At present, especially optical detectors such as an absorbance detector and a fluorescence detector are most frequently applied for reasons of a wide application range thereof and the like.
- Light absorption characteristics and the like of a sample component are susceptible to temperature. Hence, if the temperature of the mobile phase containing the sample component changes, the output of the detector is influenced by the change in temperature, so that correct analysis results cannot be obtained. In the case where the mobile phase is influenced by a temperature fluctuation in a relatively long cycle, the influence appears as a change in baseline of the detector output. In the case where the mobile phase is influenced by a temperature fluctuation in a cycle shorter than a change in baseline, the influence appears as noise. In order to avoid such influences, the temperature of the sample component (that is, the temperature of the mobile phase) at the time of detection by the detector needs to be kept constant.
- Hence, temperature control of constituent parts of the liquid chromatograph from the column to the detector is important. In the liquid chromatograph, normally, the column and the detector are each modularized, modules suited to an analysis purpose are selected and combined, and the modules are connected by a pipe, whereby desired performance is obtained. The temperatures of the modularized column and the modularized detector are controlled independently of each other.
- For example, JP-A 2010-48554 discloses a technique of controlling the temperature of a column. According to this technique, the column is housed inside of a constant temperature bath, and a temperature sensor is attached to the outer surface of the column. Electric current supplied to a heater provided in the constant temperature bath is controlled such that a value of the temperature sensor is a target temperature, whereby the temperature of the column (that is, the temperature of a mobile phase) is controlled.
- Further, JP-A 2008-256530 discloses a technique of controlling the temperature of a detector. According to this technique, a flow cell is irradiated with light emitted from a light source, and the amount of transmitted light is detected by a photodetector. This configuration includes: a sample temperature regulation block for housing the flow cell therein; and a photodetector temperature regulation block for housing the photodetector therein, and also includes a simultaneous temperature regulation block in contact with the two blocks. Then, the simultaneous temperature regulation block is regulated to a constant temperature, whereby the temperature of a mobile phase supplied to the flow cell and the temperature of the photodetector are kept constant.
- As described above, a pipe is necessary to send a mobile phase containing a sample from a column module to a detector module, and the temperature of the mobile phase fluctuates under influences of surrounding environments also when the mobile phase passes through the pipe between the column module and the detector module. In view of the above, conventionally, as shown in
FIG. 4 , apipe winding unit 42 is provided in the detector module separately from apipe 41, and thepipe winding unit 42 is placed in close contact around a temperature regulation block. A region sandwiched between two double wavy lines inFIG. 4 shows the inside of atemperature regulation block 46, where alight source 45, aflow cell 43, and aphotodetector 44 are provided. - In this configuration, even if the temperature of the mobile phase is changed by influences of surrounding environments when the mobile phase passes through the
pipe 41 between acolumn module 47 and adetector module 40, the temperature of the mobile phase is made constant by heat exchange with the temperature regulation block and the like when the mobile phase passes through thepipe winding unit 42. Accordingly, the temperature of the mobile phase supplied to theflow cell 43 is always constant, and the output of thephotodetector 44 can be prevented from being influenced. -
- [Patent Document 1] JP-A 2010-48554
- [Patent Document 2] JP-A 2008-256530
- In recent years, in high-performance liquid chromatographs (HPLCs), great importance is placed on a reduction in flow rate of a mobile phase, in order to reduce consumption of the mobile phase and a sample. Conventionally, the lowest flow rate is about several microliters/minute, whereas the flow rate is required to be reduced to about one tenth of several microliters/minute in recent years.
- If the flow rate of the mobile phase is reduced, the heat capacity of the mobile phase passing through a pipe between a column module and a detector module decreases, and influences of surrounding environments thereon increase. In the configuration of
FIG. 4 , because the heat capacity of the mobile phase is small, the temperature of the mobile phase detected by the detector is more stable. - Meanwhile, unfortunately, the amount of mobile phase is increased by the long
pipe winding unit 42, the analysis time is longer, and the sample component spreads in a flow path direction, which causes a problem of peak broadening. - An objective of the present invention is to provide a liquid sending pipe for a liquid chromatograph detector and a liquid chromatograph that are capable of always keeping the temperature of a sample component at the time of detection by the detector constant and thus preventing an influence of the temperature on the output of the detector, in a low flow rate analysis using a modularized column unit and a modularized detection unit.
- The present invention achieved to solve the aforementioned problems provides a liquid sending pipe for a liquid chromatograph detector, the liquid sending pipe being used for a liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid sending pipe including:
- a) a connection pipe for introducing a sample eluted from the column of the column module into the detection unit module; and
- b) a heat insulating member for covering an outer circumference of the connection pipe.
- The heat insulating member may include: an air layer for covering the outer circumference of the connection pipe; and a tube for covering the air layer. With this configuration, an excellent heat insulating effect of air can be used.
- The heat insulating member may include a sealing member for sealing the air layer between the connection pipe and the tube. With this configuration, the air between the connection pipe and the tube is not lost, and new air does not enter from the outside, so that the heat insulating effect can be enhanced.
- Further, the heat insulating member may include a sponge for covering an outer circumference of the tube, whereby a more excellent heat insulating effect can be obtained.
- The invention of the present application also provides a liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid chromatograph including:
- a) a connection pipe provided between the constant temperature bath and the detection unit module; and
- b) a heat insulating member for covering an outer circumference of the connection pipe.
- Moreover, in the liquid chromatograph, a lowest flow rate in a measurement range is equal to or less than 1 μL/min.
- With the liquid sending pipe for a liquid chromatograph detector and the liquid chromatograph according to the present invention, the temperature of the connection pipe is insusceptible to influences of surrounding environments due to the heat insulating effect of the heat insulating member that covers the outer circumference of the connection pipe. Hence, without the need to provide a pipe winding unit as in conventional cases, it is possible to always keep the temperature of a sample component at the time of detection by the detector constant and thus prevent an influence of the temperature on the output of the detector, in a low flow rate analysis.
- Further, the column exterior volume (here, refers to “the volume of a flow path in which a sample component is eluted from the column and is supplied to a flow cell”) can be reduced by removing the pipe winding unit. Hence, effects outside of the column, such as peak broadening, can be reduced, and an increase in speed and resolution of the liquid chromatograph can be achieved.
-
FIG. 1 is a configuration diagram of a main part of a liquid chromatograph according to an embodiment of the present invention. -
FIG. 2 is a configuration diagram of a liquid sending pipe for the liquid chromatograph detector according to the present embodiment. -
FIG. 3 is a detailed diagram of the liquid sending pipe for the liquid chromatograph detector according to the present embodiment. -
FIG. 4 is a schematic diagram of a conventional liquid chromatograph detector. -
FIG. 5A is a graph showing an experiment result when a liquid sending pipe of the present invention is not used, andFIG. 5B is a graph showing an experiment result when the liquid sending pipe of the present invention is used. - Hereinafter, a liquid sending pipe for a liquid chromatograph detector according to an embodiment of the present invention is described in detail with reference to the attached drawings.
FIG. 1 is a configuration diagram of a main part of a liquid chromatograph according to the present embodiment. In a configuration of acolumn module 25, acolumn 21 that separates each component of a sample is housed in a temperature-regulatedconstant temperature bath 20. A fan foragitation 22 and a heater forheating 23 are provided inside of theconstant temperature bath 20. Atemperature sensor 24 is provided on a surface of thecolumn 21 to regulate the temperature to be constant. - A
detection unit module 30 includes atemperature regulation block 34, and the temperature of thetemperature regulation block 34 is regulated by a heater, a temperature sensor, and the like, which are not shown. A region sandwiched between two double wavy lines inFIG. 1 represents the inside of thetemperature regulation block 34, and alight source 33, aflow cell 31, and aphotodetector 32 are provided inside thereof. Sample components eluted from thecolumn 21 and a mobile phase reach thedetection unit 30 through aconnection pipe 11, and are then supplied to the inside of theflow cell 31. Theflow cell 31 is irradiated with light from thelight source 33, the transmitted light is detected by thephotodetector 32, and the detection result is converted into light absorption characteristics of the sample components. The analysis is not limited to such measurement of light absorption characteristics, but other characteristics such as fluorescence characteristics may be measured. - According to a configuration (liquid sending pipe 10) characteristic of the invention of the present application, an outer circumference of the
connection pipe 11 between thecolumn module 25 and thedetection unit module 30 is covered with a tube 12 (FIG. 1 ). That is, anair layer 15 is formed between theconnection pipe 11 and thetube 12, and aheat insulating member 13 made of theair layer 15 and thetube 12 is provided on the outer circumference of the connection pipe 11 (FIG. 2 ). Further, a sealingmember 14 is provided at each end of theconnection pipe 11, whereby theair layer 15 is sealed between theconnection pipe 11 and the tube 12 (FIG. 3 ). The sealing member may be formed by, for example, using a heat-shrinkable tube as thetube 12 and heating and shrinking each end of the heat-shrinkable tube. Moreover, in order to enhance a heat insulating effect, the outer circumference of thetube 12 may be covered with a sponge or the like. - In order to check effects of the present embodiment, in a configuration without a pipe winding unit, an influence on the output of a detector of the liquid chromatograph was checked through an experiment for each of the cases where the liquid sending pipe of the invention of the present application was used and where the liquid sending pipe thereof was not used (that is, where only the connection pipe was used). In each experiment, a PEEK (registered trademark) pipe made of a resin was used as the connection pipe. Conventionally, a stainless-steel pipe having a relatively high heat conductivity (16.7 to 26.0 W/(m·k)), for example, is used for the material of the connection pipe, in order to enhance a heat exchange function. If a PEEK pipe having a heat conductivity that is about one tenth (0.25 to 0.92 W/(m·k)) of that of the stainless-steel pipe is used therefor, heat insulation properties can be enhanced. The inner diameter of the PEEK pipe was 0.13 mm, the outer diameter thereof was 1.6 mm, and the length of the pipe was 430 mm. Moreover, a Sumitube (registered trademark) that is a heat-shrinkable tube was used as the tube of the liquid sending pipe of the invention of the present application. The inner diameter of the Sumitube was 2.1 mm, the thickness thereof was 0.2 mm, and an air layer having a thickness of 0.25 mm was formed between the PEEK pipe and the Sumitube. The flow rate of the mobile phase of the liquid chromatograph was set to 0.6 mL/min. Further, the capacity of the flow cell and the capacity of the pipe from the column to the flow cell were each set to about one tenth of that in conventional techniques.
- The experiments were carried out in a room. The temperature of the room during the experiments slowly changed in a cycle of approximately 30 minutes due to turning on/off of an air conditioner. The fluctuation range of the room temperature at that time was about 2° C. A solution containing acetonitrile, water, and triethylamine at a ratio of 500:500:1 was used as the mobile phase of the liquid chromatograph. Triethylamine is capable of great absorption in a short wavelength region around 230 nm, and the amount of its absorption increases as the temperature rises. Hence, the mobile phase used for the experiments of this time had an absorption wavelength at 230 nm. In order to also check an influence of the absorption wavelength of the mobile phase on analytical sensitivity, data was acquired for four cases where the light wavelength of the detector used for the analysis was 350 nm, 300 nm, 250 nm, and 230 nm.
-
FIG. 5A andFIG. 5B are graphs in which the horizontal axis is time (minute) and the vertical axis is an absorbance unit (AU) calculated from the detection intensity of the detector. First, experimental data when theliquid sending pipe 10 of the present invention was not used is described. In the graph ofFIG. 5A , the detection intensity fluctuates in a relatively long cycle (about 30 minutes) (baseline fluctuation). This cycle is coincident with the fluctuation cycle of the room temperature, and it can be understood that the temperature of the mobile phase inside of theconnection pipe 11 is influenced by surrounding environments (room temperature). It can also be understood that the detection intensity fluctuates in a cycle shorter than that of the baseline fluctuation. This is considered as noise that is generated because the temperature of the mobile phase inside of the connection pipe is influenced by local fluctuations of an air convection in the liquid chromatograph. - Further, it can be understood that particularly the baseline fluctuation and the noise are larger at the absorption wavelength (230 nm) of the mobile phase.
- Next, experimental data when the
liquid sending pipe 10 of the present invention was used is described. InFIG. 5B , both the baseline fluctuation and the noise are smaller than those inFIG. 5A . Table 1 shows numerical values of the baseline fluctuation and the noise inFIG. 5A andFIG. 5B . In Table 1, values of the baseline fluctuation are calculated from a difference between a local maximum value and a local minimum value of the detection intensity in each graph. Further, values of the noise are calculated on the basis of ASTM standards E1657-96, in order to eliminate an influence of the baseline fluctuation. - In Table 1, “Without liquid sending pipe” represents values when the liquid sending pipe of the invention of the present application was not used, and “With liquid sending pipe” represents values when the liquid sending pipe of the invention of the present application was used. It is confirmed that the use of the liquid sending pipe of the invention of the present application can make both the baseline fluctuation and the noise smaller, and can suppress an influence on the output of the detector. At 230 nm that is the absorption wavelength, the noise after the countermeasures is improved to be equal to or less than one fifth of that before the countermeasures, and the baseline fluctuation after the countermeasures is improved to be equal to or less than one half of that before the countermeasures, which can sufficiently satisfy practical application.
- Although the flow rate of the mobile phase of the liquid chromatograph was 0.6 mL/min in the above-mentioned embodiment, it was also confirmed that similar effects were obtained at a flow rate of 1 μL/min or less.
-
TABLE 1 Unit Au Baseline fluctuation Noise Detector With liquid Without liquid With liquid Without liquid wavelength sending pipe sending pipe sending pipe sending pipe (350 nm) 100μ 400μ 8.02μ 9.85μ (300 nm) 100μ 300μ 8.78μ 9.91μ (250 nm) 200μ 500μ 9.59μ 12.83μ (230 nm) 2000μ 4500μ 18.46μ 96.25μ -
- 10 . . . Liquid Sending Pipe
- 11 . . . Connection Pipe
- 12 . . . Tube
- 13 . . . Heat Insulating Member
- 14 . . . Sealing Member
- 15 . . . Air Layer
- 20, 47 . . . Constant Temperature Bath
- 21 . . . Column
- 22 . . . Cooling Fan
- 23 . . . Heater for Heating
- 24 . . . Temperature Sensor
- 25, 48 . . . Column Module
- 30, 40 . . . Detection Unit
- 31, 43 . . . Flow Cell
- 32, 44 . . . Photodetector
- 41 . . . Pipe
- 42 . . . Pipe Winding Unit
- 33, 45 . . . Light Source
- 34, 46 . . . Temperature Regulation Block
Claims (7)
1. A liquid sending pipe for a liquid chromatograph detector, the liquid sending pipe being used for a liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid sending pipe comprising:
a) a connection pipe provided between the constant temperature bath and the detection unit module; and
b) a heat insulating member for covering an outer circumference of the connection pipe.
2. The liquid sending pipe for a liquid chromatograph detector according to claim 1 , wherein the heat insulating member includes: an air layer for covering the outer circumference of the connection pipe; and a tube for covering the air layer.
3. The liquid sending pipe for a liquid chromatograph detector according to claim 2 , wherein the heat insulating member includes a sealing member for sealing the air layer between the connection pipe and the tube.
4. The liquid sending pipe for a liquid chromatograph detector according to claim 2 , wherein the heat insulating member includes a sponge for covering an outer circumference of the tube.
5. The liquid sending pipe for a liquid chromatograph detector according to claim 3 , wherein the heat insulating member includes a sponge for covering an outer circumference of the tube.
6. A liquid chromatograph including: a column module in which a column is housed in a temperature-regulated constant temperature bath; and a temperature-regulated detection unit module, the liquid chromatograph comprising:
a) a connection pipe provided between the constant temperature bath and the detection unit module; and
b) a heat insulating member for covering an outer circumference of the connection pipe.
7. The liquid chromatograph according to claim 6 , wherein a lowest flow rate in a measurement range is equal to or less than 1 μL/min.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-190484 | 2012-08-30 | ||
JP2012190484A JP5915467B2 (en) | 2012-08-30 | 2012-08-30 | Liquid feeding tube for liquid chromatograph detector and liquid chromatograph |
Publications (2)
Publication Number | Publication Date |
---|---|
US20140060163A1 true US20140060163A1 (en) | 2014-03-06 |
US9835598B2 US9835598B2 (en) | 2017-12-05 |
Family
ID=50185534
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/012,227 Active 2035-06-20 US9835598B2 (en) | 2012-08-30 | 2013-08-28 | Liquid sending pipe for liquid chromatograph detector and liquid chromatograph |
Country Status (3)
Country | Link |
---|---|
US (1) | US9835598B2 (en) |
JP (1) | JP5915467B2 (en) |
CN (1) | CN103675165B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104568903A (en) * | 2014-12-31 | 2015-04-29 | 苏州普力恩企业管理咨询有限公司 | Wine liquid detection device |
US20220244223A1 (en) * | 2021-02-03 | 2022-08-04 | Shimadzu Corporation | Detector for liquid chromatograph |
US11987801B2 (en) | 2018-05-11 | 2024-05-21 | Massachusetts Eye And Ear Infirmary | Altering tissue tropism of adeno-associated viruses |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2024075410A (en) * | 2022-11-22 | 2024-06-03 | 東ソー株式会社 | Liquid chromatograph detector that suppresses noise caused by atmospheric pressure fluctuations |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2002241A (en) * | 1931-10-30 | 1935-05-21 | Diascope Corp Ltd | Electric furnace muffle construction |
US2375714A (en) * | 1942-09-03 | 1945-05-08 | Gen Electric | Butter conditioner |
US3864909A (en) * | 1971-07-28 | 1975-02-11 | Boysen Friedrich Kg | Thermal reactor with relatively movable internal pipe sections |
US3903868A (en) * | 1974-08-05 | 1975-09-09 | Anthony Salvo | Hot water boiler |
US4220136A (en) * | 1978-09-13 | 1980-09-02 | Penney Richard J | Solar energy collector |
US4269710A (en) * | 1976-01-30 | 1981-05-26 | Pye Limited | Chromatographic apparatus |
US4370826A (en) * | 1978-06-05 | 1983-02-01 | Davidson James D | Shutter shields (R), auto-mated thermal shutters for glass areas |
SU1332112A1 (en) * | 1986-02-05 | 1987-08-23 | Киевский Зональный Научно-Исследовательский И Проектный Институт Типового И Экспериментального Проектирования Жилых И Общественных Зданий | Solar heat collector |
US5039409A (en) * | 1988-09-14 | 1991-08-13 | U.S. Philips Corporation | Chromatography apparatus |
US5283995A (en) * | 1992-05-04 | 1994-02-08 | Frantz Manufacturing Company | Door light frame assembly |
US5529624A (en) * | 1994-04-12 | 1996-06-25 | Riegler; Norbert | Insulation material |
US20080047208A1 (en) * | 2006-08-22 | 2008-02-28 | Soltesiz Joseph R | Double pane window construction |
US20100223978A1 (en) * | 2009-03-06 | 2010-09-09 | Mccauley Edward B | System and Method for a Gas Chromatograph to Mass Spectrometer Interface |
US20110120213A1 (en) * | 2008-08-01 | 2011-05-26 | Shiseido Company, Ltd. | Sample injector, sample injecting method, and liquid chromatograph |
US20110186157A1 (en) * | 2001-06-13 | 2011-08-04 | Paul Phillip H | Precision Flow Control System |
US20110302994A1 (en) * | 2008-12-10 | 2011-12-15 | Anderson Jr James M | Components Suitable for Use in Devices Such as an Evaporative Light Scattering Detector |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2791970B2 (en) * | 1994-05-20 | 1998-08-27 | 有限会社島村計器製作所 | Differential refractive index detector for liquid chromatography |
JPH08129004A (en) * | 1994-10-28 | 1996-05-21 | Shimadzu Corp | Differential refractometer detector |
JPH0943201A (en) * | 1995-07-27 | 1997-02-14 | Shimadzu Corp | Liquid chromatograph mass spectrometer |
JP2000111536A (en) * | 1998-09-30 | 2000-04-21 | Shimadzu Corp | Column oven for liquid chromatograph |
JP3476417B2 (en) * | 2000-06-05 | 2003-12-10 | 株式会社島津製作所 | Analytical method by liquid chromatography |
WO2003046545A1 (en) * | 2001-11-29 | 2003-06-05 | Gl Sciences Incorporated | Separating pipe |
JP2003207491A (en) * | 2002-01-10 | 2003-07-25 | Sumitomo Wiring Syst Ltd | Size exclusion chromatography test apparatus |
JP2004093344A (en) * | 2002-08-30 | 2004-03-25 | Shiseido Co Ltd | Separate column attitude control mechanism of liquid chromatography |
US7138050B2 (en) * | 2003-05-29 | 2006-11-21 | Shimadzu Corporation | Fractionating/collecting device of liquid chromatograph |
CN1749750A (en) * | 2004-09-13 | 2006-03-22 | 聂智明 | High efficiency liquid phase chromatograph |
CN200953015Y (en) * | 2005-10-21 | 2007-09-26 | 刘开禄 | Constant temperature industrial liquid phase chromatograph system |
JP4569633B2 (en) * | 2006-02-09 | 2010-10-27 | 株式会社島津製作所 | Analysis method and apparatus by liquid chromatography |
JP4935225B2 (en) * | 2006-07-28 | 2012-05-23 | 株式会社島津製作所 | Electronic component assembly |
JP2008256530A (en) * | 2007-04-05 | 2008-10-23 | Shimadzu Corp | Fluorescence detector and liquid chromatography equipped with same |
JP2010048554A (en) | 2008-08-19 | 2010-03-04 | Shimadzu Corp | Column temperature monitoring apparatus and chromatographic apparatus |
JP2011013151A (en) * | 2009-07-03 | 2011-01-20 | Shimadzu Corp | Sample heating device |
JP5471900B2 (en) * | 2010-07-01 | 2014-04-16 | 株式会社島津製作所 | Liquid chromatograph |
CN202177307U (en) * | 2010-12-31 | 2012-03-28 | 苏州新长光热能科技有限公司 | Novel track type mechanical charging device |
CN102141488B (en) * | 2011-03-15 | 2012-07-04 | 重庆大学 | Preparative gas-phase chromatograph device for separating and purifying high-boiling-point volatile monomer component |
-
2012
- 2012-08-30 JP JP2012190484A patent/JP5915467B2/en active Active
-
2013
- 2013-08-28 US US14/012,227 patent/US9835598B2/en active Active
- 2013-08-30 CN CN201310389258.0A patent/CN103675165B/en active Active
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2002241A (en) * | 1931-10-30 | 1935-05-21 | Diascope Corp Ltd | Electric furnace muffle construction |
US2375714A (en) * | 1942-09-03 | 1945-05-08 | Gen Electric | Butter conditioner |
US3864909A (en) * | 1971-07-28 | 1975-02-11 | Boysen Friedrich Kg | Thermal reactor with relatively movable internal pipe sections |
US3903868A (en) * | 1974-08-05 | 1975-09-09 | Anthony Salvo | Hot water boiler |
US4269710A (en) * | 1976-01-30 | 1981-05-26 | Pye Limited | Chromatographic apparatus |
US4370826A (en) * | 1978-06-05 | 1983-02-01 | Davidson James D | Shutter shields (R), auto-mated thermal shutters for glass areas |
US4220136A (en) * | 1978-09-13 | 1980-09-02 | Penney Richard J | Solar energy collector |
SU1332112A1 (en) * | 1986-02-05 | 1987-08-23 | Киевский Зональный Научно-Исследовательский И Проектный Институт Типового И Экспериментального Проектирования Жилых И Общественных Зданий | Solar heat collector |
US5039409A (en) * | 1988-09-14 | 1991-08-13 | U.S. Philips Corporation | Chromatography apparatus |
US5283995A (en) * | 1992-05-04 | 1994-02-08 | Frantz Manufacturing Company | Door light frame assembly |
US5529624A (en) * | 1994-04-12 | 1996-06-25 | Riegler; Norbert | Insulation material |
US20110186157A1 (en) * | 2001-06-13 | 2011-08-04 | Paul Phillip H | Precision Flow Control System |
US20080047208A1 (en) * | 2006-08-22 | 2008-02-28 | Soltesiz Joseph R | Double pane window construction |
US7681369B2 (en) * | 2006-08-22 | 2010-03-23 | Soltesiz Joseph R | Double pane window construction |
US20110120213A1 (en) * | 2008-08-01 | 2011-05-26 | Shiseido Company, Ltd. | Sample injector, sample injecting method, and liquid chromatograph |
US20110302994A1 (en) * | 2008-12-10 | 2011-12-15 | Anderson Jr James M | Components Suitable for Use in Devices Such as an Evaporative Light Scattering Detector |
US20100223978A1 (en) * | 2009-03-06 | 2010-09-09 | Mccauley Edward B | System and Method for a Gas Chromatograph to Mass Spectrometer Interface |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104568903A (en) * | 2014-12-31 | 2015-04-29 | 苏州普力恩企业管理咨询有限公司 | Wine liquid detection device |
US11987801B2 (en) | 2018-05-11 | 2024-05-21 | Massachusetts Eye And Ear Infirmary | Altering tissue tropism of adeno-associated viruses |
US20220244223A1 (en) * | 2021-02-03 | 2022-08-04 | Shimadzu Corporation | Detector for liquid chromatograph |
US11782031B2 (en) * | 2021-02-03 | 2023-10-10 | Shimadzu Corporation | Detector for liquid chromatograph |
Also Published As
Publication number | Publication date |
---|---|
JP5915467B2 (en) | 2016-05-11 |
CN103675165A (en) | 2014-03-26 |
CN103675165B (en) | 2015-11-18 |
JP2014048119A (en) | 2014-03-17 |
US9835598B2 (en) | 2017-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11273390B2 (en) | Techniques for thermally insulating a liquid chromatographic column | |
US9835598B2 (en) | Liquid sending pipe for liquid chromatograph detector and liquid chromatograph | |
US11185795B2 (en) | Techniques for thermally insulating a chromatographic column | |
US4518700A (en) | Method and apparatus for regulating the temperature of an analytical instrument reactor | |
JP4569633B2 (en) | Analysis method and apparatus by liquid chromatography | |
US11351477B2 (en) | Techniques for accelerating thermal equilibrium in a chromatographic column | |
US8410434B1 (en) | Thermo-stabilized nano- and micro- flow LC/ESI-MS interface and a method thereof | |
US8613216B2 (en) | Dynamic thermal focusing of chromatographic separations | |
US20200203141A1 (en) | Apparatus and System for Active Heat Transfer Management in Ion Sources | |
Nováková et al. | High‐resolution peptide separations using nano‐LC at ultra‐high pressure | |
JP2014048119A5 (en) | ||
Lauer et al. | Advances in capillary electrophoresis: the challenges to liquid chromatography and conventional electrophoresis | |
Gritti | A Look at Vacuum-Jacketed Columns: Maximum Efficiency, Easy Deployment Without Oven, and Improved LC–MS Performance | |
US6601439B2 (en) | Method of reducing baseline instabilities in liquid chromatographic measurements and liquid chromatography apparatus | |
US11994500B2 (en) | Techniques for temperature control of separation devices and optical detection devices of mass analysis systems | |
CN109416348B (en) | Techniques for thermally insulating chromatography columns | |
US5658446A (en) | Preparative capillary electrophoresis with wide-bore capillary | |
JPH041557A (en) | Flow cell of infrared spectrophotometer | |
JP3846013B2 (en) | Liquid chromatograph | |
JPH01182749A (en) | Mass spectrograph apparatus for liquid chromatography | |
JPH0266445A (en) | Electron capturing type detector for chromatograph | |
JPH0555057U (en) | Electrochemical detector |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SHIMADZU CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WATANABE, MASATO;GUNJI, MASAHIDE;REEL/FRAME:032368/0482 Effective date: 20130902 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |